Chemistry 5.12 Spring 2003 Lectures #1 & 2, 2/5,7/03

1. Chemistry 5.12 Spring 2003 Lectures #1 & 2, 2/5,7/03 Outline • Discuss General Class Information (Professor Imperiali) • General Introduction to Organic Chemistry • I. Review of Lewis Bonding Theory (Read Chapter 1) • A. Ionic Bonding (1-3A,6,8) • B. Covalent Bonding (1-3B,4) • 1. Multiple Bonding (1-5) • 2. Formal Charge (1-7) • C. Short-Hand for Chemists • 1. Line-Angle Formulas: Simplified Structures (1-10) • 2. Dashes and Wedges: Molecules in 3-D (2-5) • 3. Curved Arrow Formalism: Electrons in Motion (1-14) • II. Resonance (1-9) • A. Rules for Drawing Resonance Structures • B. Relative Energy of Resonance Structures • C. Structure and Reactivity from Resonance • Suggested Problems: 1-25,36,39,41 Problem Set #1 Posted: Due Monday 2/10 by 4pm

2. Organic Chemistry 5.12 Spring 2003 Prof. Barbara Imperiali Dr. Sarah Tabacco • Text:Organic Chemistry, L.G. Wade, Jr., 5th Ed. • Recitations:Twice a week, beginning second week. Section changes should be made through the 5.12 website. All changes must be made by Friday 2/14. • Problem Sets:Turn in to TA's box in Chem. Ed. office by 4pm on the due date. Lowest grade will be dropped. No late work accepted. • Midterms:During class period. Lowest grade will be dropped. No make-up exams. • Exam #1 Friday, 2/21 • Exam #2 Friday 3/14 • Exam #3 Monday, 4/14 • Exam #4 Monday, 5/5 • Grading:Upon request, exams can be regraded within one week. Problem sets will not be regraded. Problem Sets: 10% Midterm Exams: 50% Final Exam: 40%

3. Organic Chemistry: What is it? • 1780: Organic compounds very complex and only obtained from living sources (vitalism) • Vitalism: Belief that a "magic" vital force, present in plants and animals, is necessary for the synthesis of organic compounds • 1789: Antoine Laurent Lavoisier observed that organic compounds are composed primarily of carbon and hydrogen • 1828: Friedrich Wohler synthesized an organic compound (urea) from inorganic compounds (lead cyanate and ammonium hydroxide). Modern organic chemistry is the chemistry of carbon compounds.

4. "The Age of Organic Chemistry" • > 95% of All Known Compounds Composed of Carbon • Organic Chemistry Crucial to Our Way of Life: Clothing, Materials (Polymers), Petroleum, Medicine, OUR BODIES • > 50% of Chemists Are Organic MECHANISM SYNTHESIS STRUCTURE Understanding the Reactivity of Molecules: How and Why Chemical Reactions Take Place Building Complex Molecules From Simple Molecules Using Chemical Reactions Determining the Way in Which Atoms Are Put Together in Space to Form Complex olecules

5. Why Carbon? • • Carbon forms a variety of strong covalent bonds to itself and other atoms. • This allows organic compounds to be structurally diverse. Why Does Carbon Bond in This Way?

6. I. Review of Lewis Bonding Theory(READ CH 1) • Atoms transfer or share electrons to gain a filled valence shell of electrons. A. Ionic Bonding • Between atoms of widely different electronegativity (ΔEN>2); usually a metal and a non-metal; atoms held together by electrostatic attraction, not electron sharing

7. B. Covalent Bonding (Electron Sharing) • Very important in organic molecules! • Between atoms of similar electronegativity; usually non-metallic lone pair: unshared electron pair; non-bonding pair of electrons How can you tell how many bonds and how many lone pairs an atom will have?

8. Count the Valence Electrons!

9. 1. Multiple Bonding • Two atoms can share more than one pair of electrons to gain a filled shell (very common in organic molecules)

10. 2. Formal Charge • Not all atoms are neutral in a Lewis or Kekule structure • Formal charges help chemists to keep track of the placement of electrons in molecules • Does not indicate that all of the charge is actually localized on one atom Always indicate formal charge on problem sets and exams!

11. Summary of Bonding (Charged Atoms) Be able to recognize common bonding patterns.

12. C. Short-Hand for Chemists: Easy Communication1. ine-Angle Formulas: Drawing Complex Molecules Quickly Brevetoxin A (!!)

13. Rules for Drawing Line-Angle Formulas • Bonds are represented by lines (one line = two shared electrons) • Do not draw carbon or hydrogen atoms, except at termini (for aesthetics) • Assume carbon atoms are at ends of lines and where they meet • Assume enough C–H bonds to give each carbon atom four bonds (an octet) • Draw heteroatoms and attached hydrogen atoms (N,O,S,P,F,Cl,Br,I, etc.)

14. 2. Using Dashes and Wedges: Molecules Are Not Flat! • Tetra-Substituted Carbon Is Tetrahedral (more on this later).

15. Representing Molecules • Lewis/Kekule Structures: Represent atoms sharing electrons to form bonds • Line-Angle Structures: Simplify the drawing of complex molecular structures • Dashes and Wedges: Allow chemists to draw molecules in 3-D BUT! These simplified structures do not accurately represent the electronic nature or reactivity of organic molecules! • It helps to think about electrons in motion . . .BUT HOW DO WE REPRESENT ELECTRONS IN MOTION?

16. 3. Curved Arrow Formalism (Arrow Pushing) • Chemists use arrows to represent the motion of electrons within and between molecules.

18. Chemical reactions generally involve the movement of electrons between two or more molecules, but electrons also move within a molecule. • The reactivity of a molecule is not always explained by one Lewis structure. • Molecules can be thought of as hybrids or weighted averages of two or more Lewis structures, each with a different placement of electrons. • These structures, called resonance structures, are not real or detectable, but they are a useful conceptual tool for understanding the reactivity of molecules. II. Resonance: Electronic Motion Within a Molecule

20. A. Rules for Drawing Resonance Structures • Only electrons move! Nuclei and the sigma- (single bond-) framework are unchanged (Resonance occurs in the pi-system: conjugated lone pairs and pi-bonds). • Every resonance structure must be a valid Lewis structure. • Keep track of lone pairs and formal charges. • Use arrow-pushing formalism to interconvert and identifiy possible resonance structures. • Always use double-headed arrow ( ) in between resonance structures. • Lowerenergy resonance structures contribute most to the overall structure of the molecule. How do you predict the relative energies of resonance structures?

21. B. Guidelines for Predicting Energies of Resonance Structures (In Order of Importance) i) Filled Octets: Second row elements (C, N, O , F) want an octet (filled valence shell of electrons). Because C is the least electronegative, structures in which C has 6 electrons, 3 bonds and a positive charge are possible (not possible with N, O, F). ii) Negative charges on most electronegative atoms. iii) Minimize charge separation.

22. A: follows guidelines B: violates iii: 2 formal charges C: violates ii &iii: negative charge on C; 2 formal charges D: violates i&iii: 6 electrons on C; 2 formal charges E: violates i&iii: 6 electrons on C; 2 formal charges

23. Delocalization of Charge = Stabilization The conjugate base of phenol (phenoxide) is stabilized by resonance. Because phenoxide ion is stabilized, phenol is more acidic than cyclohexanol. • In general, the more resonance structures there are, the greater the stabilization. • Equivalent resonance structures provide more stabilization than inequivalent ones.

24. C. Structure and Reactivity Info from Resonance Structures • Drawn this way, benzene appears to have two types of carbon– carbon bonds (single and double). • Experimental data indicates that all of the carbon–carbon bonds in benzene are equivalent and rather unreactive. • Benzene is approximately 35 kcal/mol more stable than would be expected because the electrons are delocalized around the ring. e.g. Benzene